Fungicidal anilides

ABSTRACT

Use of an anilide of the formula: ##STR1## as a fungicidal agent against phytophatogenic fungi, particularly their strains resistant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides.

This invention relates to fungicidal anilides.

Benzimidazole and thiophanate fungicides such as Benomyl (methyl 1-(butylcarbamoyl)benzimidazol-2ylcarbamate), Fubelidazol (2-(2-furyl)benzimidazole), Thiabendazole (2-(4-thiazolyl)benzimidazole), Carbendazim (methyl benzimidazol-2-ylcarbamate), Thiophanate-methyl (1,2-bis(3-methoxycarbonyl-2-thioureido)benzene), Thiophanate (1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene), 2-(O,S-dimethylphosphorylamino)-1-(3'-methoxycarbonyl-2'-thioureido)benzene and 2-(O,O-dimethylthiophosphorylamino)-1-(3'-methoxycarbonyl-2'-thioureido)benzene exhibit an excellent fungicidal activity against various plant pathogenic fungi, and they have been widely used as agricultural fungicides since 1970. However, their continuous application over a long period of time allows phytopathogenic fungi to develop a tolerance to them, whereby their plant disease-preventive effect is significantly decreased. Further, the fungi which developed tolerance to certain kinds of benzimidazole or thiophanate fungicides also exhibit considerable tolerance to some other kinds of benzimidazole or thiophanate fungicides. Thus, they are apt to develop cross-tolerance. Therefore, if any material decrease of their plant disease-preventive effect in certain fields is observed, their application to such fields has to be discontinued. But, it is often observed that the density of drug-resistant organisms is not reduced even long after the discontinuation of the application. Although other kinds of fungicides have to be employed in such a case, only few are so effective as benzimidazole or thiophanate fungicides in controlling various phytopathogenic fungi. Benzimidazole and thiophanate fungicides are hereinafter referred to as "benzimidazole thiophanate fungicides". Cyclic imide fungicides such as Procymidone (3-(3', 5'-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide), Iprodione (3-(3', 5'-dichlorophenyl)-1-isopropylcarbamoylimidazolidine-2,4-dione), Vinchlozolin (3-(3', 5'-(dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione), ethyl (RS)-3-(3', 5'-dichlorophenyl)-5-methyl-2,4-dioxooxazolidine-5-carboxylate, etc., which are effective against various plant diseases, particularly those caused by Botrytis cinerea, have the same defects as previously explained with respect to the benzimidazole thiophanate fungicides.

As a result of study seeking a new type of fungicides, it has now been found that anilides of the formula: ##STR2## wherein X and Y are, same or different, each a halogen atom, a lower alkyl group, a lower alkenyl group, a lower cyanoalkenyl group, a lower alkynyl group, a lower alkoxy group, a cyano group, a lower alkyl group substituted with at least one member selected from the group consisting of halogen, hydroxyl and cyano, or a group of the formula: ##STR3## in which R₂ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower haloalkyl group, R₃ and R₄ are, same or different, each a hydrogen atom or a lower alkyl group and n is 2, 3 or 4; Z is a hydrogen atom, a fluorine atom or a group of the formula: OR₅ in which R₅ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkyl group substituted with at least one member selected from the group consisting of halogen, lower alkoxy and lower cycloalkyl; and R₁ is a C₁ -C₇ alkyl group, a C₂ -C₆ alkenyl group, a C₂ -C₆ alkynyl group, a C₃ -C₇ cycloalkyl group, a C₁ -C₆ haloalkyl group, a lower haloalkenyl group, a lower alkyl group substituted with at least one member selected from the group consisting of cyano, lower alkoxy, lower cycloalkyl and phenoxy (phenoxy being optionally substituted with at least one halogen and/or at least one alkyl), a phenyl group, a phenyl group substituted with at least one member selected from the group consisting of halogen, cyano, nitro, trifluoromethyl, lower alkyl and lower alkoxy or an aralkyl group (aralkyl being optionally substituted with at least one halogen and/or at least one alkyl) exhibit an excellent fungicidal activity against plant pathogenic fungi which have developed resistance to benzimidazole thiophanate fungicides and/or cyclic imide fungicides. It is notable that their fungicidal potency against the organisms tolerant to benzimidazole thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drug-resistant fungi" or "drug-resistant strains") is much higher than that against the organisms sensitive to benzimidazol thiophanate fungicides and/or cyclic imide fungicides (hereinafter referred to as "drug-sensitive fungi" or "drug-sensitive strains").

The term "lower" used hereinabove and hereinafter in connection with organic radicals or compounds indicates that such radicals or compounds each have not more than 4 carbon atoms. The term "halogen"used hereinabove and hereinafter indicates fluorine, chlorine, bromins or iodine.

Typical examples of the anilides of the formula (I) are shown in Table 1.

                                      TABLE 1                                      __________________________________________________________________________      ##STR4##                                                                      X         Y       Z          R.sup.1                                           __________________________________________________________________________     CH.sub.3  CH.sub.3                                                                               H                                                                                          ##STR5##                                         C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                        H          CHCHCH.sub.3                                      OCH.sub.3 OCH.sub.3                                                                              H                                                                                          ##STR6##                                         Cl        Cl      F          C.sub.3 H.sub.7 (iso)                             CH.sub.3  CH.sub.3                                                                               OCH.sub.3  C.sub.3 H.sub.7 (n)                               Cl        Cl      OC.sub.2 H.sub.5                                                                           ##STR7##                                         Cl        Cl      OCH.sub.2 CF.sub.3                                                                         ##STR8##                                         CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          CH.sub.3                                          CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                   CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               CH.sub.3   CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          CHCH.sub.2                                        CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           ##STR9##                                         CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          CHCHCH.sub.3                                      CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           ##STR10##                                        CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           ##STR11##                                        Cl        OCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CH.sub.3                                          Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                   Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.4 H.sub.9 (n)                               Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.4 H.sub.9 (sec)                             Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.4 H.sub.9 (iso)                             Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CHCH.sub.2                                        Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR12##                                        Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CHCHCH.sub.3                                      Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR13##                                        Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR14##                                        Cl        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CH.sub.2 OCH.sub.3                                Cl        OC.sub.2 H.sub.5                                                                       OC.sub.3 H.sub.7 (n)                                                                      C.sub.2 H.sub.5                                   Cl        OC.sub.2 H.sub.5                                                                       OCH.sub.2 CHCH.sub.2                                                                      C.sub.3 H.sub.7 (iso)                             Cl        OC.sub.2 H.sub.5                                                                        ##STR15## CHCHCH.sub.3                                      Cl        OC.sub.2 H.sub.5                                                                       OCH.sub.2 CH.sub.2 OCH.sub.3                                                               ##STR16##                                        Cl        OC.sub.2 H.sub.5                                                                       OCH.sub.2 CH.sub.2 Cl                                                                     C.sub.3 H.sub.7 (n)                               Cl        OC.sub.2 H.sub.5                                                                       OCH.sub.2 CCH                                                                              ##STR17##                                        Br        OCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                           ##STR18##                                        CH.sub.3  OCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CH.sub.3                                          CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                   CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.4 H.sub.9 (sec)                             CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.4 H.sub.9 (iso)                             CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.4 H.sub.9 (tert)                            CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CHCH.sub.2                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR19##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CHCHCH.sub.3                                      CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR20##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR21##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR22##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CH.sub.2 Cl                                       CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CH.sub.2 OCH.sub. 3                               CH.sub.2 CHCH.sub.2                                                                      CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               CCH       OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                                ##STR23##                                                                               OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR24##                                        CN        OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             OCH.sub.3 OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          CHCHCH.sub.3                                      COOCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               COCH.sub.3                                                                               OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                   CHO       OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                              ##STR25##                                                                               OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             CHNOCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             CH.sub.2 OCH.sub.3                                                                       OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR26##                                        CONHCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR27##                                        Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          CH.sub.3                                          Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                   Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          CHCHCH.sub.3                                      Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                           ##STR28##                                        Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          CH.sub.2 CH.sub.2 Cl                              Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          CH.sub.2 CN                                       Cl        CH.sub.2 OCH.sub.3                                                                      OC.sub.2 H.sub.5                                                                          ##STR29##                                        Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                           ##STR30##                                        CH.sub.3  CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                   CH.sub.3  CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (n)                               CH.sub.3  CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             CH.sub.3  CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          CHCHCH.sub.3                                      CH.sub.3  CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                           ##STR31##                                        Cl        Cl      H                                                                                          ##STR32##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR33##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                          C.sub.5 H.sub.11 (n)                              CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR34##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR35##                                        CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           ##STR36##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR37##                                        Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                           ##STR38##                                        CH.sub.3  OC.sub.2 H.sub.5                                                                       OC.sub.2 H.sub.5                                                                           ##STR39##                                        Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                           ##STR40##                                        CH.sub.2 CHCH.sub.2                                                                      CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             Cl        OC.sub.2 H.sub.5                                                                       OCH.sub.2 CH.sub.2 Cl                                                                      ##STR41##                                        Cl        CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           ##STR42##                                        Cl        OC.sub.2 H.sub. 5                                                                      OCH.sub.2 CHCH.sub.2                                                                      C.sub.2 H.sub.5                                   Cl        Cl      OCHF.sub.2                                                                                 ##STR43##                                        Cl        Cl      F          C.sub.2 H.sub.5                                   Cl        CH.sub.2 OCH.sub.3                                                                     OC.sub.2 H.sub.5                                                                          CH.sub.2 Cl                                       C.sub.3 H.sub.7 (n)                                                                      OCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             Cl        CH.sub.2 OCH.sub.3                                                                     OCH.sub.2 CCH                                                                              ##STR44##                                        COC.sub.2 H.sub.5                                                                        CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                          CHCHCH.sub.3                                      CHCHCH.sub.3                                                                             OCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          C.sub.3 H.sub.7 (iso)                             Cl        Cl      OC.sub.2 H.sub.5                                                                           ##STR45##                                        CH.sub.3  CH.sub.3                                                                               OC.sub.2 H.sub.5                                                                           ##STR46##                                        __________________________________________________________________________

Some of the anilides (I) have hitherto been synthesized; for instance, N-(3-bromo-4,5-dimethoxyphenyl)acetamide (C.A., 49, 10234a), N-(3-acetyl-4-allyloxy-5-propylphenyl)acetamide (C.A., 54, 8732d), N-(3,5-dichloro-4-methoxyphenyl)-2-bromoacetamide (C.A., 84, 164487z), N-(3,5-dichloro-4-ethoxyphenyl)-2-methylpropanamide (ibid.) and so on are known. Several of them have been known to exhibit antipyretic or herbicidal activity. However, it has not been known or reported that they have fungicidal activity or are useful as fungicides.

Thus, the present invention provides a fungicidal composition which comprises, as an active ingredient, a fungicidally effective amount of the anilide of the formula (I) and an inert carrier or diluent. It also provides a combination composition comprising as active ingredients the anilide of the formula (I) together with a benzimidazole thiophanate fungicide and/or a cyclic imide fungicide, which is fungicidally effective against not only drug-sensitive fungi but also drug-resistant fungi, and hence particularly effective for the prevention of plant diseases. It also provides a method of controlling plant pathogenic fungi including drug-resistant strains and drug-sensitive strains by applying a fungicidally effective amount of the anilide of the formula (I) to plant pathogenic fungi.

Further, it provides nove anilides which are representable by the formula: ##STR47## wherein X and Y are, same or different, each a halogen atom, alower alkyl group, a lower alkenyl group, a lower cyanoalkenyl group, a lower alkynyl group, a lower alkoxy group, a cyano group, a lower alky group substituted with at least one member selected from the group consisting of halogen, hydroxyl and cyano, or a group of the formula: ##STR48## in which R₂ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower haloalkyl group, R₃ and R₄ are, same or different, each a hydrogen atom or a lower alkyl group and n is 2, 3 or 4; Z is a fluoride atom or a group of the formula: OR₅ in which R₅ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group or a lower alkyl group substituted with at least one member selected from the group consisting of halogen, lower alkoxy and lower cycloalkyl; and R₁ is a C₂ -C₇ alkyl group, a C₂ -C₆ alkenyl group, a C₂ -C₆ alkynyl group, a C₃ -C₇ cycloalkyl group, a C₂ -C₆ haloalkyl group, a lower haloalkenyl group, a lower alkyl group substituted with at least one member selected from the group consisting of cyano, lower alkoxy, lower cycloalkyl and phenoxy (phenoxy being optionally substituted with at least one halogen and/or at least one alkyl), a phenyl group, a phenyl group substituted with at least one member selected from the group consisting of halogen, cyano, nitro, trifluoromethyl, lower alkyl and lower alkoxy or an aralkyl group (aralkyl being optionally substituted with at least one halogen and/or at least one alkyl), with the provisos that when X and Y are same and represent chlorine or bromine, Z is neither methoxy nor ethoxy, that X, Y and Z are not simultaneously methoxy, and that when X and Y are same and represent chlorine and Z is fluorine, R₁ is neither isopropyl nor isopropenyl. It furthermore provides a process for producing the novel anilides.

Accccording to the present invention, the anilides (I) can be prepared by reacting a 3,4,5-trisubstituted aniline of the formula: ##STR49## wherein X, Y and Z are each as defined above, with a carboxylic acid of the formula: ##STR50## wherein R₁ is as defined above or its reactiv derivative at the carboxyl group such as a carboxylic acid halide of the formula: ##STR51## wherein R₁ is as defined above and B is a halogen atom or a carboxylic acid anhydride of the formula: ##STR52## wherein R₁ is as defined above.

The starting 3,4,5-trisubstituted aniline (II) can be produced by a known procedure (cf. EP-A-0063905) or any analogous procedure thereto.

The anilides (I) are fungicidally effective against a wide scope of plant pathogenic fungi, of which examples are as follows: Podosphaera leucotricha, Venturia inaequalis, Mycosphaerella pomi, Marssonina mali and Sclerotinia mali of apple, Phyllactinia kakicola and Gloeosporium kaki of persimmon, Cladosporium carpophilum and Phomopsis sp. of peach, Cercospora viticola, Uncinula necator, Elsinoe ampelina and Glomerella cingulata of grape, Cercospora beticola of sugarbeet, Cercospora arachidicola and Cercospora personata of peanut, Erysiphe graminis f. sp. hordei, Cercosporella herpotrichoides and Fusarium nivale of barley, Erysiphe graminis f. sp. tritici of wheat, Sphaerotheca fuliginea and Cledosporium cucumerinum of cucumber, Cladosporium fulvum of tomato, Corynespora melogenae of eggplant, Sphaerotheca humuli, Fusarium oxysporum f. sp. fragariae of strawberry, Botrytis alli of onion, Cercospora apii of cerely, Phaeoisariopsis griseola of kidney bean, erysiphe cichoracearum of tobacco, Diplocarpon rosae of rose, Elsinoe fawcetti, Penicillium italicum, Penicillium digitatum of orange, Botrytis cinerea of cucumber, eggplant, tomato, strawberry, pimiento, onion, lettuce, grape, orange, cyclamen, rose or hop, Sclerotinia sclerotiorum of cucumber, eggplant, pimiento, lettuce, celery, kidney bean, soybean, azuki bean, potato or sunflower, Sclerotinia cinerea of peach or cherry, Mycosphaerella melonis of cucumber or melon, etc. Namely, the anilides (I) are highly effective in controlling the drug-resistant strains of the fungi.

The anilides (I) are also fungicidally effective against fungi to which known fungicides are ineffective. Examples of such fungi are Pyricularia oryzae, Pseudoperonospora cubensis, Plasmopara viticola, Phytophthora infestans, etc.

Advantageously, the anilides (I) are low in toxicity and have little detrimental effects on mammals and so on. Also, they may be applied to an agricultural field without causing any material toxicity to important crop plants.

Typical examples of the procedure for preparation of the anilides (I) are shown in the following examples.

EXAMPLE 1

Preparation of N-(3,5-dimethyl-4-ethoxyphenyl)-2-butenamide

To a solution of 2-butenoic acid (0.86 g) in tetrahydrofuran (30 ml), 3,5-dimethyl-4-ethoxyaninline (1.65 g) was added, and a solution of N,N'-dicyclohexylcarbodiimide (D.C.C.) (2.2 g) in tetrahydrofuran (20 ml) was dropwise added threto while stirring. After 30 minutes, the by-produced N,N'-dicyclohexylurea (D.C.U.) was removed by filtration. To the filtrate was added acetic acid (2 ml) to decompose excessive D.C.C., followed by filtration of D.C.U. The resultant filtrate was poured into ice-water and extracted with ether. The extract was washed with 1N hydrochloric acid, sodium bicarbonate solution and saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography using hexane-acetone as the eluent to give N-(3,5-dimethyl-4-ethoxyphenyl)-2butenamide (Compound No. 12) (2.17 g) in a yield of 93%. M.P., 118°-119° C.

EXAMPLE 2

Preparation of N-(3,4-diethoxy-5-methylphenyl)cyclopropanecarboxamide 3,4-Diethoxy-5-methylaniline (1.95 g) and triethylamine (1.01 g) were dissolved in toluene (20 ml). To the rsultant solution was dropwise added cyclopropanecarboxylic acid chloride (1.05 g) in 10 minutes under ice-cooling. After being stirred at room temperature for 5 hours, the reaction mixture was poured into ice water and extracted with toluene. The extract was washed with 1N hydrochloric acid, sodium bicaarbonate solution and saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude crystals (2.55 g). Recrystallization from ethanol gave N-(3,4-diethoxy)-5-methylphenyl)cyclopropanecarboxamide (Compound No. 44) (2.32 g) in a yield of 88%. M.P., 120°-121° C.

In the same manner as above, the anilides of the formula (I) as shown in Table 2 can be prepared:

                                      TABLE 2                                      __________________________________________________________________________      ##STR53##                                                                     Compound                                                                       No.   X        Y      Z         R.sup.1    Physical constant                   __________________________________________________________________________      1    CH.sub.3 CH.sub.3                                                                              H                                                                                         ##STR54## M.P. 123-124° C.              2    OCH.sub.3                                                                               OCH.sub.3                                                                             H                                                                                         ##STR55## M.P. 114-115° C.              3    Cl       Cl     F         C.sub.3 H.sub.7 (iso)                                                                     M.P. 195-196° C.              4    Cl       Cl     OC.sub.2 H.sub.5                                                                          ##STR56## M.P. 153-155° C.              5    Cl       Cl     OCH.sub.2 CF.sub.3                                                                        ##STR57## M.P. 155-156° C.              6    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         CH.sub.3   M.P. 132-133° C.              7    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub. 5                                                                        C.sub.2 H.sub.5                                                                           M.P. 99-100° C.               8    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       M.P. 78-79° C.                9    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 121-122° C.             10    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         CHCH.sub.2 M.P. 82-83.5° C.             11    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          ##STR58## M.P. 75-76° C.               12    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         CHCHCH.sub.3                                                                              M.P. 118-119° C.             13    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          ##STR59## M.P. 148-149° C.             14    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          ##STR60## M.P. 153-154° C.             15    Cl       OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       M.P. 81.5-83° C.             16    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CH.sub.3   M.P. 106-107° C.             17    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                           M.P. 101-102° C.             18    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       M.P. 80-81° C.               19    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     n.sub.D.sup.26 1.5241               20    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.4 H.sub.9 (n)                                                                       M.P. 66-67° C.               21    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.4 H.sub.9 (sec)                                                                     M.P. 102-103° C.             22    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.4 H.sub.9 (iso)                                                                     M.P. 91-92° C.               23    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CHCH.sub.2 M.P. 106-107° C.             24    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR61## n.sub.D.sup.24 1.5452               25    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CHCHCH.sub.3                                                                              M.P. 95-96° C.               26    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR62## M.P. 102-104° C.             27    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR63## M.P. 80-81° C.               28    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CH.sub.2 OCH.sub.3                                                                        wax                                 29    Cl       OC.sub.2 H.sub.5                                                                      OC.sub.3 H.sub.7 (n)                                                                     C.sub.2 H.sub.5                                                                           M.P. 95-96° C.               30    Cl       OC.sub.2 H.sub.5                                                                      OCH.sub.2 CHCH.sub.2                                                                     C.sub.3 H.sub.7 (iso)                                                                     M.P. 50-53° C.               31    Cl       OC.sub.2 H.sub.5                                                                      OCH.sub.2 CH.sub.2 Cl                                                                    C.sub.3 H.sub.7 (n)                                                                       M.P. 84-86° C.               32    Cl       OC.sub.2 H.sub.5                                                                      OCH.sub.2 C CH                                                                            ##STR64## M.P. 73-75° C.               33    Br       OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                          ##STR65## M.P. 119-120° C.             34    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CH.sub.3   M.P. 87.5-89° C.             35    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                           M.P. 89.5-91° C.             36    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.2 H.sub.7 (n)                                                                       M.P. 44-46° C.               37    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 92-93° C.               38    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.4 H.sub.9 (sec)                                                                     M.P. 91-92.5° C.             39    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.4 H.sub.9 (tert)                                                                    M.P. 127-128° C.             40    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub. 5                                                                        CHCH.sub.2 M.P. 82-83° C.               41    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR66## M.P. 51.5-53° C.             42    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CHCHCH.sub.3                                                                              M.P. 85-86.5° C.             43    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR67## M.P. 134-135° C.             44    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR68## M.P. 120-121° C.             45    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR69## M.P. 117-118° C.             46    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CH.sub.2 Cl                                                                               M.P. 120-121° C.             47    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         CH.sub.2 OCH.sub.3                                                                        n.sub.D.sup.26 1.5185               48    CH.sub.2 CH CH.sub.2                                                                    CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       n.sub.D.sup.24 1.5302               49    CCH      OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       M.P. 83-84° C.               50    COOCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       M.P. 67-68° C.               51    CHO      OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 98.5-100° C.            52    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         CH.sub.3   M.P. 99-100° C.              53    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                           M.P. 58-59° C.               54    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       N.sub.D.sup.23.5 1.5346             55    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 82-83° C.               56    Cl        CH.sub.2 OCH.sub.3                                                                   OC.sub.2 H.sub.5                                                                         CHCHCH.sub.3                                                                              n.sub.D.sup.24 1.5571               57    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                          ##STR70## M.P. 109-110° C.             58    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         CH.sub.2 CH.sub.2 Cl                                                                      M.P. 81-82° C.               59    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                          ##STR71## M.P. 110-111° C.             60    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                          ##STR72## M.P. 88-89° C.               61    CH.sub.3 CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                           M.P. 68-69° C.               62    CH.sub.3 CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (n)                                                                       n.sub.D.sup.25 1.5171               63    CH.sub.3 CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 122-123° C.             64    CH.sub. 3                                                                               CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         CHCHCH.sub.3                                                                              n.sub.D.sup.25 1.5347               65    CH.sub.3 CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                          ##STR73## n.sub.D.sup.25 1.5369               66    Cl       Cl     H                                                                                         ##STR74## M.P. 169-170° C.             67    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR75## M.P. 108-109.5° C.           68    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.5 H.sub.11 (n)                                                                      n.sub.D.sup.26 1.5040               69    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR76## M.P. 130-133° C.             70    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR77## M.P. 136-137° C.             71    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          ##STR78## M.P. 108-109° C.             72    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub. 5                                                                         ##STR79## M.P. 91-92.5° C.             73    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                          ##STR80## M.P. 96-97° C.               74    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                          ##STR81## M.P. 92-93° C.               75    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                          ##STR82## n.sub.D.sup.26 1.5246               76    CH.sub.2 CHCH.sub.3                                                                     CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 85-86° C.               77    Cl       OC.sub.2 H.sub.5                                                                      OCH.sub.2 CH.sub.2 Cl                                                                     ##STR83## M.P. 122-123° C.             78    Cl       CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          ##STR84## M.P. 141.5-143° C.           79    Cl       OC.sub.2 H.sub.5                                                                       OCH.sub.2 CHCH.sub.2                                                                    C.sub.2 H.sub.5                                                                           M.P. 83-84° C.               80    Cl       Cl     OCHF.sub.2                                                                                ##STR85## M.P. 140-141° C.             81    Cl       Cl     F         C.sub.2 H.sub.5                                                                           M.P. 132-133.5° C.           82    Cl       CH.sub.2 OCH.sub.3                                                                    OC.sub.2 H.sub.5                                                                         CH.sub.2 Cl                                                                               M.P. 49-51° C.               83    C.sub.3 H.sub.7 (n)                                                                     OCH.sub.3                                                                             OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 92-93.5° C.             84    Cl       CH.sub.2 OCH.sub.3                                                                    OCH.sub.2 CCH                                                                             ##STR86## n.sub.D.sup.24 1.5952               85    COC.sub.2 H.sub.5                                                                       CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                         CHCHCH.sub.3                                                                              n.sub.D.sup.27 1.5591               86    CHCHCH.sub.3                                                                            OCH.sub.3                                                                             OC.sub.2 H.sub. 5                                                                        C.sub.3 H.sub.7 (iso)                                                                     M.P. 97.5-98.5° C.           87    Cl       OC.sub.2 H.sub.5                                                                      OCH.sub.2 CH.sub.2 OCH.sub.3                                                              ##STR87## M.P. 78-81° C.               88    CH.sub.3 OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.4 H.sub.9 (iso)                                                                     wax                                 89    CN       OC.sub.2 H.sub.5                                                                      OC.sub.2 H.sub.5                                                                         C.sub.3 H.sub.7 (iso)                                                                     M.P. 101-102° C.             90    Cl       Cl     OC.sub.2 H.sub.5                                                                          ##STR88## M.P. 84-86° C.               91    CH.sub.3 CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                          ##STR89## M.P. 121-123° C.             __________________________________________________________________________

In the practical use of the anilides (I) as fungicides, they may be applied as such or in a formulation form such as dusts, wettable powders, oil sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols or flowables. Such a formulation form can be formulated in a conventional manner by mixing at least one of the anilides (I) with an appropriate solid or liquid carrier(s) or diluent(s) and, if necessary, an appropriate adjuvant(s) (e.g. surfactants, adherents, dispersants, stabilizers) for improving the dispersibility and other properties of the active ingredient.

Examples of the solid carriers or diluents are botanical materials (e.g. flour, tobacco stalk powder, soybean powder, walnut-shell powder, vegetable powder, saw sust, bran, bark powder, cellulose powder, vegetable extract residue), fibrous materials (e.g. paper, corrugated cardboard, old rags), synthetic plastic powders, clays (e.g. kaolin, bentonite, fuller's earth), talcs, other inorganic materials (e.g. pyrophyllite, sericite, pumice, sulfur powder, active carbon) and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride). Examples of the liquid carriers or diluents are water, alcohols (e.g. methanol, ethanol), ketones (e.g. acetone, methylethylketone), ethers (e.g. diethyl ether, dioxane, cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methyl naphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, lamp oil), esters, nitriles, acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, carbon tetrachloride), etc.

Examples of the surfactants are alkyl sulfuric esters, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc. Examples of the adherents and dispersants may include cesein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil and agar. As the stabilizers, there may be used PAP (isopropyl acid phosphate mixture), tricresyl phosphate (TCP), tolu oil, epoxydized oil, various surfactants, various fatty acids and their esters, etc.

The foregoing formulations generally contain at least one of the anilides (I) in a concentration of about 1 to 95% by weight, preferably of 2.0 to 80% by weight. By using the formulations, the anilides (I) are generally applied in such amounts as 2 to 100 g per 10 are.

When only the drug-resistant strains of phytopathogenic fungi are present, the anilides (I) may be used alone. However, when the drug-sensitive strains are present together with the drug-resistant strains, their alternate use with benzimidazole thiophanate fungicides and/or cyclic imide fungicides or their combined use with benzimidazole thiophanate fungicides and/or cyclic imide fungicides is favorable. In such an alternate or combined use, each active ingredient may be employed as such or in conventional agricultural formulation forms. In case of the combined use, the weight proportion of the anilide (I) and the benzimidazole thiophanate fungicide and/or the cyclic imide fungicide may be from about 1:0.1 to 1:10.0.

Typical examples of the benzimidazole thiophanate fungicides and the cyclic imnide fungicides are shown in Table 3.

                                      TABLE 3                                      __________________________________________________________________________     Compound                                                                             Structure            Name                                                __________________________________________________________________________            ##STR90##           Methyl 1-(butylcarbamoyl)benz-  imidazol-2-ylca                                rbamate                                             B                                                                                     ##STR91##           2-(4-Thiazolyl)benzimidazole                        C                                                                                     ##STR92##           Methyl benzimidazol-2-ylcarbamate                   D                                                                                     ##STR93##           2-(2-Furyl)benzimidazole                            E                                                                                     ##STR94##           1,2-Bis(3-methoxycarbonyl-2-thio-                                              ureido)benzene                                      F                                                                                     ##STR95##           1,2-Bis(3-ethoxycarbonyl-2-thio-                                               ureido)benzene                                      G                                                                                     ##STR96##           2-(O,SDimethyl- phosphorylamino)-1- (3'-methoxy                                carbonyl- 2'-thioureido)benzene                     H                                                                                     ##STR97##           2-(O,ODimethylthio- phosphorylamino)-1-                                        (3'-methoxycarbonyl- 2'-thioureido)benzene          I                                                                                     ##STR98##           N(3',5'-Dichloro- phenyl)-1,2-dimethyl-                                        cyclopropane-1,2-dicarboximide                      J                                                                                     ##STR99##           3-(3',5'-Dichloro- phenyl)-1-isopropyl-                                        carbamoylimidazolidine-2,4-dione                    K                                                                                     ##STR100##          3-(3',5'-Dichlorophenyl)-5-methyl-5-  vinyloxaz                                olidine-2,4-dione                                   L                                                                                     ##STR101##          Ethyl (RS)3-(3',5'- dichlorophenyl)-5-methyl-2,                                4-dioxo-  oxazolidine-5-carboxylate                 __________________________________________________________________________

Besides, the anilides (I) may be also used ub admixture with other fungicides, herbicides, inseciticides, miticides, fertilizers, etc.

When the anilides (I) are used as fungicides, they may be applied in such amounts as 2 to 100 grams per 10 ares. However, this amount may vary depending upon formulation forms, application times, application methods, application sites, diseases, crops and so on, and therefore, they are not limited to particalar amounts.

Some practical embodiments of the fungicidal composition according to the invention are shown in the following Examples wherein % and part(s) are by weight.

FORMULATION EXAMPLE 1

Two parts of Compound No. 9, 88 parts of clay and 10 parts of talc are thoroughly pulverized and mixed together to obtain a dust formulation containing 2% of the active ingredient.

FORMULATION EXAMPLE 2

Fifty parts of Compound No. 25, 25 parts of diatomaceous earth, 20 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of calcium ligninsulfonate as a dispersing agent are mixed while being powdered to obtain a wettable powder formulation containing 50% of the active ingredient.

FORMULATION EXAMPLE 3

Twenty-five parts of Compound No. 37, 50 parts of Compound I, 18 parts of diatomaceous earth, 3.5 parts of calcium alkylbenzenesulfonate as a wetting agent and 3.5 parts of calcium ligninsulfonate as a dispersing agent are mixed while being powdered to obtain a wettable powder formulation containing 75% of the active ingredient.

FORMULATION EXAMPLE 4

Twenty parts of Compound No. 44, 30 parts of Compound A, 40 parts of powdery sucrose, 5 parts of white carbon, 3 parts of sodium laurylsulfate as a wetting agent and 2 parts of clacium ligninsulfonate as a dispersing agent are mixed while being powdered to obtain a wettable powder formulation containing 50% of the active ingredient.

Typical test data indicating the excellent fungicidal activity of the anilides (I) are shown below. The compounds used for comparison are as follows:

    ______________________________________                                         Compound            Remarks                                                    ______________________________________                                         Benomyl             Commercially available                                      ##STR102##         fungicide                                                  Thiophanate-methyl  Commercially available                                      ##STR103##         fungicide                                                  Carbendazim         Commercially available                                      ##STR104##         fungicide                                                  Thiabendazole       Commercially available                                      ##STR105##         fungicide                                                  ______________________________________                                    

EXPERIMENT 1

Protective Activity Test on Powdery Mildew of Cucumber (Sphaerotheca fuliginea)

A flower pot of 90 ml volume was filed with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. Thedegree of damage was determined in the following manner, and the results are shown in Table 4.

The leaves examined were measured for a percentage of infected area and classified into the corresponding disease indices, 0, 0.5, 1, 3, 4:

    ______________________________________                                         Disease index Percentage of infected area                                      ______________________________________                                         0             No infection                                                     0.5           Infected area of less than 5%                                    1             Infected area of less than 20%                                   2             Infected area of less than 50%                                   4             Infected area of not less than 50%                               ______________________________________                                    

The disease severity was calculated according to the following equation: ##EQU1##

The prevention value was calculated according to the following equation: ##EQU2##

                  TABLE 4                                                          ______________________________________                                                                Prevention Prevention                                                          value when value when                                             Concentration                                                                               inoculated inoculated                                             of active    with drug- with drug-                                   Compound  ingredient   resistant  sensitive                                    No.       (ppm)        strain (%) strain (%)                                   ______________________________________                                          9        200           97        0                                            12        200           97        0                                            13        200          100        0                                            19        200          100        0                                            25        200          100        0                                            26        200          100        0                                            42        200           97        0                                            44        200          100        0                                            Benomyl   200           0         100                                          Thiophanate-                                                                             200           0         100                                          methyl                                                                         Carbendazim                                                                              200           0         100                                          ______________________________________                                    

As understood from the results shown in Table 4, the anilides (I) of the invention exhibit an excellent preventive effect on the drug-resistant strain but do not exhibit any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl, Thiophanate-methyl and Carbendazim exhibit a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain. Other tested compounds structurally similar to the anilides (I) do not exhibit any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.

EXPERIMENT 2

Preventive Effect on Cercospora Leaf Spot of Sugarbeet (Cercospora beticola)

A flower pot of 90 ml volume was filled with sandy soil, and seeds of sugarbeet (var: Detroit dark red) were sowed therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Cercospora beticola by spraying. The pot was covered with a polyvinyl chlorid sheet to make a condition of high humidity, and cultivation was continued in the greenhouse for 10 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 5.

                  TABLE 5                                                          ______________________________________                                                                Prevention Prevention                                                          value when value when                                             Concentration                                                                               inoculated inoculated                                             of active    with drug- with drug-                                   Compound  ingredient   resistant  sensitive                                    No.       (ppm)        strain (%) strain (%)                                   ______________________________________                                         13        200           97        0                                            18        200           97        0                                            19        200          100        0                                            25        200          100        0                                            44        200          100        0                                            Benomyl   200           0         100                                          Thiophanate-                                                                             200           0         100                                          methyl                                                                         Carbendazim                                                                              200           0         100                                          ______________________________________                                    

As understood from the results shown in Table 5, the anilide (I) of the invention exhibit an excellent preventive effect on the drug-resistant strain but do not exhibit any preventive effect on the tested drug-sensitive strain. To the contrary, commecially available known fungicides such as Benomyl, Thiophanate-methyl and Carbendazim exhibit a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain. Other tested compounds structurally similar to the anilides (I) do not exhibit any fungicidal activity on the drug-sensitive strain and the drug-resistant strain.

EXPERIMENT 3

Preventive Effect on Scab of Pear (Venturia nashicola)

A plastic pot of 90 ml volume was filled with sandy soil, and seeds of pear (var: Chojuro) were sowed therein. Cultivation was carried out in a greenhouse for 20 days. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a spore suspension of the drug-resistant or drug-sensitive strain of Venturia nashicola by spraying. The resulting plants were placed at 20° C. under a condition of high humidity for 3 days and then at 20° C. under irradiation with a fluorescent lamp for 20 days. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 6.

                  TABLE 6                                                          ______________________________________                                                                Prevention Prevention                                                          value when value when                                             Concentration                                                                               inoculated inoculated                                             of active    with drug- with drug-                                   Compound  ingredient   resistant  sensitive                                    No.       (ppm)        strain (%) strain (%)                                   ______________________________________                                         12        200           94        0                                            19        200          100        0                                            36        200          100        0                                            42        200           97        0                                            44        200          100        0                                            Benomyl   200           0         100                                          Thiophanate-                                                                             200           0         100                                          methyl                                                                         ______________________________________                                    

As understood from the results shown in Table 6, the anilides (I) of the invention exhibit an excellent preventive effect on the drug-resistant strain but do not exhibit any preventive effect on the tested drug-sensitive strain. To the contrary, commercially available known fungicidee such as Benomyl and Thioophanate-methyl exhibit a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

EXPERIMENT 4

Preventive Effect on Gray Mold of Cucumber (Botrytis cinerea)

Plastic pots of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation was carried out in a greenhouse for 8 days to obtain cucumber seedlings expanding cotyledons. Onto the resulting seedlings, the test compound formulated in emulsifiable concentrate or wettable powder and diluted with water was sprayed at a rate of 10 ml per pot. After air-drying, the seedlings were inoculated with mycelial disks (5 mm in diameter) of the drug-resistant or drug-sensitive strain of Botrytis cinerea by putting them on the leaf surfaces. After the plants were infected by incubating under high humidity at 20° C. for 3 days, the rates of disease severity were observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 7.

                  TABLE 7                                                          ______________________________________                                                                Prevention Prevention                                                          value when value when                                             Concentration                                                                               inoculated inoculated                                             of active    with drug- with drug-                                   Compound  ingredient   resistant  sensitive                                    No.       (ppm)        strain (%) strain (%)                                   ______________________________________                                          1        200          88         0                                             2        200          88         0                                             3        500          88         0                                             4        200          94         0                                             5        200          88         0                                             6        200          96         0                                             7        200          94         0                                             8        200          100        0                                             9        200          100        0                                            10        200          96         0                                            11        200          88         0                                            12        200          100        0                                            13        200          100        0                                            14        200          88         0                                            15        200          100        0                                            16        200          92         0                                            17        200          100        0                                            18        200          100        0                                            19        200          100        0                                            20        200          100        0                                            21        200          100        0                                            22        200          100        0                                            23        200          100        0                                            24        200          98         0                                            25        200          100        0                                            26        200          100        0                                            27        200          98         0                                            28        200          94         0                                            29        200          100        0                                            30        200          100        0                                            31        200          100        0                                            32        200          100        0                                            33        200          88         0                                            34        200          88         0                                            35        200          94         0                                            36        200          97         0                                            37        200          100        0                                            38        200          100        0                                            39        200          92         0                                            40        200          100        0                                            41        200          88         0                                            42        200          100        0                                            43        200          97         0                                            44        200          100        0                                            45        200          92         0                                            46        200          100        0                                            47        200          94         0                                            48        200          100        0                                            49        200          100        0                                            50        200          88         0                                            51        200          100        0                                            52        200          88         0                                            53        200          94         0                                            54        200          100        0                                            55        200          100        0                                            56        200          100        0                                            57        200          94         0                                            58        200          98         0                                            59        200          98         0                                            60        200          88         0                                            61        200          88         0                                            62        200          94         0                                            63        200          100        0                                            64        200          100        0                                            65        200          100        0                                            66        500          94         0                                            67        500          88         0                                            68        200          100        0                                            69        200          100        0                                            70        500          96         0                                            71        200          98         0                                            72        200          100        0                                            73        200          100        0                                            74        200          100        0                                            75        200          92         0                                            76        200          100        0                                            77        200          100        0                                            78        200          100        0                                            79        200          100        0                                            80        500          98         0                                            81        500          88         0                                            82        500          92         0                                            83        200          100        0                                            84        500          94         0                                            85        500          92         0                                            86        200          100        0                                            87        200          98         0                                            88        200          94         0                                            89        200          100        0                                            90        200          98         0                                            91        200          100        0                                            Benomyl   200          0          100                                          Thiophanate-                                                                             200          0          100                                          methyl                                                                         ______________________________________                                    

As understood from the results shown in Table 7, the anilides (I) of the invention exhibit an excellent preventive effect on the drug-resistant stain but do not exhibit any preventive effect onto the tested drug-sensitive strain. To the contrary, commercially available known fungicides such as Benomyl and Thiophanate-methyl exhibit a notable controlling effect on the drug-sensitive strain but not on the drug-resistant strain.

EXPERIMENT 5

Preventive Effect on Powdery Mildew of Cucumber (Sphaerotheca fuliginea)

A plastic pot of 90 ml volume was filled with sandy soil, and seeds of cucumber (var: Sagami-hanjiro) were sowed therein. Cultivation was carried out in a greenhouse for 8 days. Onto the resulting seedlings having cotyledons, the test compound(s) formulated in emulsifiable concentrate or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Sphaerotheca fuliginea by spraying and further cultivated in the greenhouse. Ten days thereafter, the infectious state of the plants was observed. The degree of damage was determined in the same manner as in Experiment 1, and the results are shown in Table 8.

                  TABLE 8                                                          ______________________________________                                                       Concentration of                                                                            Prevention                                                        active ingredient                                                                           value                                               Compound No.  (ppm)        (%)                                                 ______________________________________                                         19            100          34                                                  19             20          0                                                   25            100          42                                                  25             20          0                                                   37            100          42                                                  37             20          0                                                   42            100          44                                                  42             20          0                                                   44            100          45                                                  44             20          0                                                   A             100          44                                                  A              20          19                                                  B             500          45                                                  B             100          10                                                  C             100          44                                                  C              20          12                                                  D             500          36                                                  D             100          0                                                   E             100          42                                                  E              20          10                                                  F             100          45                                                  F              20          8                                                   G             100          42                                                  G              20          8                                                   H             100          40                                                  H              20          5                                                   19 + A        20 + 20      100                                                 19 + B        20 + 20      100                                                 19 + E        20 + 20      100                                                 19 + G        20 + 20      100                                                 25 + C        20 + 20      100                                                 25 + D        20 + 20      100                                                 25 + F        20 + 20      100                                                 25 + H        20 + 20      100                                                 37 + A        20 + 20      100                                                 37 + D        20 + 20      100                                                 37 + E        20 + 20      100                                                 37 + G        20 + 20      100                                                 42 + A        20 + 20      100                                                 42 + B        20 + 20      100                                                 42 + E        20 + 20      100                                                 42 + G        20 + 20      100                                                 44 + B        20 + 20      100                                                 44 + C        20 + 20      100                                                 44 + E        20 + 20      100                                                 44 + H        20 + 20      100                                                 ______________________________________                                    

As understood from the results shown in Table 8, the combined use of the anilides (I) of the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides exhibit a much more excellent preventive effect than their sole use.

EXPERIMENT 6

Preventive Effect on Gray Mold of Tomato (Botrytis cinerea)

A plastic pot of 90 ml volume was filled with sandy soil, and seeds of tomato (var: Fukuji No. 2) were sowed therein. Cultivation was carried out in a greenhouse for 4 weeks. Onto the resulting seedlings at the 4-leaf stage, the test compound(s) formulated in emulsifiable concentrated or wettable powder and diluted with water were sprayed at a rate of 10 ml per pot. Then, the seedlings were inoculated with a mixed spore suspension of the drug-resistant and drug-sensitive strain of Botrytis cinerea by spraying and placed at 20° C. in a room of high humidity for 5 days. The degree of damge was determined in the same manner as in Experiment 1, and the results are shown in Table 9.

                  TABLE 9                                                          ______________________________________                                                       Concentration of                                                                            Prevention                                                        active ingredient                                                                           value                                               Compound No.  (ppm)        (%)                                                 ______________________________________                                         18            100          28                                                  18             20           0                                                  25            100          34                                                  25             20           0                                                  44            100          42                                                  44             20           0                                                  I             100          48                                                  I              20          22                                                  J             500          44                                                  J             100          18                                                  K             100          42                                                  K              20          12                                                  L             500          45                                                  L             100          10                                                  18 + I        20 + 50      100                                                 18 + J        20 + 50      100                                                 25 + I        20 + 50      100                                                 25 + K        20 + 50      100                                                 44 + I        20 + 50      100                                                 44 + J        20 + 50      100                                                 44 + K        20 + 50      100                                                 44 + L        20 + 50      100                                                 ______________________________________                                    

As understood from the results shown in Table 9, the combined use of the anilides (I) of the invention with benzimidazole thiophanate fungicides and/or cyclic imide fungicides exhibit a much more excellent preventive effect than their sole use. 

What is claimed is:
 1. A fungicidal composition which comprises as an active ingredient a fungicidally effective amount of an anilide of the formula: ##STR106## wherin X is halogen; Z and Y are a lower alkoxy group; and R₁ is a C₁ -C₇ alkyl group or a C₂ -C₆ alkenyl group; and an inert carrier.
 2. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR107##
 3. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR108##
 4. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR109##
 5. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR110##
 6. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR111##
 7. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR112##
 8. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR113##
 9. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR114##
 10. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR115##
 11. The fungicidal composition as recited in claim 1, wherein the anilide is represented by the formula: ##STR116##
 12. A method for controlling plant pathogenic fungi which comprises applying a fungicidally effective amount of at least one of the anilides of the formula: ##STR117## wherein X, Y, Z and R₁ are each as defined in claim 1, to plant pathogenic fungi.
 13. The method according to claim 12, wherein the plant pathogenic fungi is the drug-resistant strain. 